Lecithin mixtures and reaction products of 1 2-disubstituted imidazoline

ABSTRACT

THE MIXTURE AND REACTION PRODUCT OF LECITHIN AND CERTAIN 1,2-DISUBSTITUTED IMIDAZOLINES ARE USEFUL AS GASOLINE ANTIWEAR AND ANTIFILTER-CLOGGING AGENTS.

United States Patent 3,644,393 LECITHIN MIXTURES AND REACTION PRODUCTS0F 1,2-DISUBSTITUTED IMIDAZOLINE Helen I. Thayer, Oakmont, Pa., assignorto Gulf Research & Development Company, Pittsburgh, Pa. No Drawing.Continuation-impart of application Ser. No. 544,838, Apr. 25, 1966. Thisapplication Aug. 29, 1969, Ser. No. 854,277

' Int. Cl. C07d 49/34 U.S. Cl. 260309.6 2 Claims ABSTRACT OF THEDISCLOSURE The mixture and reaction product of lecithin and certain1,2-disubstituted imidazolines are useful as gasoline antiwear andantifilter-clogging agents.

This application is a continuation-in-part of Ser. No. 544,838, filedApr. 25, 1966, now US. Pat. No. 3,527,583.

This invention relates to multipurpose additives for motor fuels, tomotor fuel compositions containing a minor proportion of said additives,and to methods of improving the performance of gasoline-burning engineswith said compositions. The additives of the present invention performtwo primary functions in gasoline including (1) reduction of wear incast iron piston rings of a gasoline-burning engine and (2) reduction ofthe tendency of gasoline to clog a fuel filter element.

The antiwear and antifilter-clogging gasoline additives 0f the presentinvention comprise either a mixture of or the reaction product oflecithin and a 1,2-disubstituted imidazoline. The imidazoline has analkylamine substituent in the 1-position and an alkyl substituentcontaining 7 to 29 carbon atoms in the 2-position. A preferred1,2-disubstituted imidazoline of this invention is prepared by reactingdiethylene triamine and a mixture of saturated and unsaturated fattyacids to produce predominantly a 1-(2- aminoethyl)-2-alkylimidazolinehaving the general formula In the absence of lecithin, the1,2-disubstituted imidazolines utilized in this invention impart an onlypartially beneficial effect when added to gasoline. The1,2-disubstituted imidazolines per se impart antiwear properties togasoline as evidenced by reduction in loss of metallic iron from castiron piston rings. However, when the 1,2-disubstituted imidazolines areeither mixed with or reacted with lecithin the product exerts anadditional highly beneficial effect in gasoline, i.e. substantialreduction of the tendency of the gasoline to clog the filter throughwhich it passes in its flow to an engine. The lecithin imidazolines ofthis invention probably reduce filter clogging by completely dissolvingsome of the dispersed solids in gasoline and by partially dissolvingother dispersed solids to reduce the size thereof.

The antifilter-clogging characteristic is highly important because innearly all automobiles, motor fuels are filtered during flow to anengine. Furthermore, reducing the level of solids in gasoline in itselftends to decrease wear of piston rings by reducing abrasion at saidpiston rings.

3,644,393 Patented Feb. 22, 1972 Therefore, the antiwear andantifilter-clogging characteristics of the additives of this inventioncooperate to produce a common advantageous effect: the antiwear functioncontributing directly to piston ring wear rate reduction and theantifilter-clogging function contributing indirectly to reduction ofengine wear by completely dissolving a portion of the potentiallyabrasive solids in gasoline and by partially dissolving another portionof said solids to reduce the size thereof, thereby permitting easierremoval of the remaining solids by filtration.

The antifilter-clogging characteristic of both the mixture of and thereaction product of lecithin and the 1,2- disubstituted imidazolinesutilized in this invention is unexpected because neither lecithin byitself nor the imidazolines by themselves impart antifilter-cloggingcharacteristics to gasoline. On the other hand, gasoline compositionscontaining either the unreacted mixture of or the reaction product oflecithin and the 1,2-disubstituted imidazolines of the invention exhibithigh antifilter-clogging characteristics.

It is significant that imidazolines differing from the imidazolines ofthe present invention only by the addition of a methyl substituent tothe imidazoline ring do not exhibit antiwear properties. While thereaction product of diethylene triamine and a fatty acid produces al,2-disubstituted imidazoline which is a highly effective antiwearagent, the reaction product of dipropylenetriamine and the same fattyacid produces a 1,2,4 or 1,2,5-trisubstituted imidazoline containing amethyl substituent in either the 4 or 5 position of the imidazoline ringwhich is not an effective antiwear agent. Therefore, while N CH:

is an effective antiwear agent, the compound 17) N OH2 CH' NH2 N CH2 CH2Ca 6H,

and methyl isomers thereof are not antiwear agents. Additionalcomparisons of the characteristics of closely rated compounds are foundin applications Ser. No. 544,- 839 and Ser. No. 544,840, both entitledMotor Fuel Multipurpose Agents and filed on the same date as thisapplication by the same inventor.

The 1,2-disubstituted imidazolines of this invention have the generalformula wherein A highly.effective commercialimidazoline whose; major.

component is 1- (Z-aminoethyl) -2-heptadecenylimidazoline having theformula is prepared by reacting a mixture of long chain fatty acids withdiethylenetriamine. Another imidazoline can be prepared by reacting afatty acid having 8 to 30 carbon atoms with N-aminomethylethylenediamine. The fatty acid mixture used in the synthesis of theabove-mentioned commercial imidazoline comprised 37.0 percent linoleicacid, 6.0 percent conjugated linoleic acid, 52.5 percent oleic acid, 0.5percent palmitic acid, 0.5 percent palmitoleic acid, 2.5 percent stearicacid, and 1.0 percent of other acids. Other suitable acids that can beused in the synthesis include lauric, myristic, arachidic, behenic,cerotic and lignoceric acids.

Examples of suitable 1,2-disubstituted imidazoline compounds of thisinvention include 1- (2'-aminoethyl -2-undecylimidazoline,

1- 2'-aminoethyl) -2-heptadecylimidazoline,

1- (2'-aminoethyl -2-tridecylimidazoline,

1- (2'-aminoethyl -2- 8"-heptadecenyl -imidazoline,

1-(2'-N,N-dimethylaminoethyl)-2-(8",11"-heptadecadienyl imidazoline,

1-(2-N-methylaminomethyl -2-pentadecylimidazoline andl-aminomethyl-Z-heneicosylimidazoline.

Any commercial lecithin can be utilized in accordance with thisinvention, such as lecithin derived from soybean oil, corn oil, linseedoil or egg yolk.

A particular commercial lecithin which was advantageously both mixedwith and reacted with an imidazoline as described above is a neutral oilsolution of a filtered soybean lecithin with a moisture value less than0.75 percent by Weight, an acetone-insoluble value of 70 percent byweight and a viscosity of 3046 centipoises. According to one method ofpreparation of the lecithin derivative of the 1,2-disubstitutedimidazolines, base lecithin is reacted with the imidazoline at 5580 C.for 19 to 55 hours while stirring the reaction mixture. In onesynthesis, grams of 1-(Z-aminoethyl)-Z-heptadecenylimidazoline and 60grams of the commercial base lecithin were heated at 55-80 C. for 19hours. The conditions of reaction of the base lecithin with the1,2-disubstituted imidazoline are not critical and a wide range ofreaction conditions can be utilized. In general, the reaction can becarried out at a temperature between about 40 C. to 100 C. for a timeduration of about 5 to 100 hours.

As stated, the conditions for reaction of the lecithin with theimidazoline are not critical. For example, while temperatures of 40 to100 C. are ordinarily suitable at atmospheric pressure, if the reactionis performed under a vacuum much higher temperatures can be employed.Also, a reaction time duration greater than 100 hours can be employed.The ratio of lecithin to imidazoline is also not critical and can varywithin wide limits. For example, the ratio can be between about 1 to 20and about 20 to 1. All of these conditions are non-limiting and arepresented for illustrative purposes only.

The concentration of the lecithin-imidazoline derivative or the mixtureof lecithin and imidazoline in gasoline is not critical. For example, anadditive of this invention can be present in gasoline in a generalconcentration range of 0.1 to 100 pounds per 1000 barrels, or apreferred concentration range of 1 to pounds per 1000 barrels. In termsof weight percentage, an additive of this invention can be present ingasoline in a general range of .00004 to .04 percent or a preferablerange of .0004 to .01 percent. If the additive comprises'a mixture oflecithin and imidazoline, the ratio of lecithin to imidazoline can varywidely. For example, the ratio of'lecithin to imidazoline can be withinthe range 1:2 to 20: 1, generally, or within the range 2:1 to 8:1,preferably.

The gasoline compositions of this invention contain as the hydrocarbonportion thereof any of the known gasoline hydrocarbons, such as, forexample, hydrocarbons boiling in the range of about 90 to 400 or 425 F.The hydrocarbon portion of the gasoline compositions can contain normal,branched-chain, and cyclic hydrocarbons having from 4 to 12 carbonatoms. The hydrocarbons portion of the gasoline compositions cancomprise products prepared in the chemical conversion of hydrocarbons toproduce gasoline such as the products prepared by isomerization,alkylation, polymerization, cracking, disproportionation, hydrogenation,dehydrogenation, and combinations of such processes. A common gasolinecomposition contains a major proportion of the gasoline hydrocarbonsprepared by fluid catalytic cracking and a minor proportion of analkylate prepared from isobutane and C and/ or C olefins. The base fuelcan comprise about percent of gasoline from the fluid catalytic-crackingprocess, and about 20 percent of the aforementioned alkylate.

EXAMPLE 1 Radioactive piston ring wear tests were performed todemonstrate the high antiwear characteristics of a gasoline containing acompound of this invention and to also demonstrate the criticality ofthe chemical structure of the additives of this invention. Following isa description of the test procedure employed in the radioactive pistonring wear tests.

Test procedure Each radioactive ring wear test was performed with a CLRlaboratory test, 4-stroke, single cylinder internal combustion engineequipped with a cast iron top compression ring which prior to use hadbeen rendered radioactive by insertion into the pile of an atomicreactor. The engine provided with the radioactive ring was operated atconstant speed for 10 hours under the following test conditions.

Speed: r.p.m. 2000.

Load: BHP 5.

Spark 15 before top center.

Air-fuel ratio l3.7/l.0.

Cylinder wall temp., F 112.

Sump oil temp. F 125.

Carburetor: Intake air temp.: F 85.

During the test the motor oil accumulated particles of the radioactivemetal lost by the radioactive piston ring through wear. The radioactivemetal content of the motor oil was continuously counted by means of aGeiger counter and recorded. At intervals oil samples were taken and theamount of dilution of oil by fuel was determined. Since dilution of oilby fuel tends to depress the radioactivity measurement, the amount ofWear was calculated on the basis of radioactivity counts corrected by afactor corresponding to the amount of dilution of the motor oil withfuel.

Table 1 shows the results of radioactive piston ring wear tests madewith a gasoline sample containing 1-(2-aminoethyl)-2-heptadecenylimidazoline, which is a 1,2- disubstitutedimidazoline of this invention, and with separate gasoline samplescontaining the imidazoline reac tion products of long chain fatty acidsand ethoxylated and nonethoxylated diproplyene triamine, both of whichare trisubstituted rather than disubstituted imidazolines and thereforenot irnidazolines of this invention. As shown by the structural formulaein Table 1, the I-(Z-aminoethyl)-2-heptadecenylimidazoline of thisinvention differs primarily from the reaction product of long chainfatty acids and dipropylene triamine only by the absence of a methylgroup on the imidazoline ring.

TABLE 1.RADIOACTIVE PISTON RING WEAR TESTS Percent change Additive inpiston ring concentrawear rate as tion, grams compared to per gallonreference Additive of gasoline gasoline1-(2-aminoethyD-Z-heptadeceriylimidazoline e 0. 270 33 The reactionproduct of long chain fa y acids and dipropylene triamine b 0. 140 +5The reaction product of long chain fatty acids and dipropylene triamineplus 2 mols of ethylene oxide 0. 140 38 a The structural formula is-'(Ci7)C--N-CH2CHzNH2 N CH2 b A mixture comprising in major proportion: l

(Cn)(;JNOHzCHNHg N CH1 CH (IJH CH3 and methl isomer thereof.

A mixture comprising in major proportion:

(C17)fiNCHzCHNH(CHzCH2O)2H and methyl isomers thereof, and/orcorresponding imidazolines wherein two separate hydroxyethyl groups areattached to the side chain mtrogen.

Table 1 shows that the disubstituted imidazoline of this inventionreduced the piston ring wear rate 33 percent as compared to a referencegasoline sample, while a trisubstituted imidazoline differing from theimidazoline of this invention primarily only by the addition of a methylgroup to the imidazoline ring was not an antiwear agent and actuallyincreased the piston ring wear rate by 5 percent. Table 1, also showsthat thetrisubstituted imidazoline can be transformed into an effectiveantiwear agent by adding ethylene oxide thereto, a procedure which addsconsiderably to the cost of. the additive as compared to thenonethoxylated imidazoline of this invention. Furthermore, it is shownin Example 2, below, that the addition of ethylene oxide to thedisubstituted imidazoline of this invention actually deprives saidimidazoline of its antiwear properties. Example 2 therefore reinforcesthe showing of criticality of the structure of disubstitutedimidazolines as compared to trisubstituted imidazolines in regard toantiwear properties.

EXAMPLE 2 Table 2 shows the results of further radioactive piston ringwear tests. The tests of Table 2 compare the antiwear properties ofgasolines containing ethoxylated and nonethoxylated disubstitutedimidazolines of this invention prepared by reaction of fatty acids whichdiethylene triamine, with the antiwear properties of gasoline containingethoxylated and nonethoxylated trisubstituted imidazolines prepared byreaction of fatty acids with dipropylene triamine, which are notadditives of this invention.

As shown in Table 2, the disubstituted imidazoline of this invention isan antiwear agent in the nonethoxylated state, but is not an antiwearagent when ethoxylated. On the other hand, trisubstituted imidazoline isnot an antiwear agent when nonethoxylated but must be ethoxylated to beconverted to an antiwear agent. Because di-substituted imidazolines areeffective antiwear agents in the nonalkoxylated state they are lessexpensive antiwear agents for gasoline than the trisubstitutedimidazolines which require alkoxylation for impartation of antiwearcharacteristics.

TABLE 2.-RADIOACTIVE PISTON RING WEAR TESTS Concen- Control,

tration, iron wear, Fuel additive p.p.m. Piston rings Oil mg. Test, ironwear, mg. The reaction product of long chain fatty acids and diethyl-98. 5 Radioactive Base motor oil free 8. 7 6.1.

ene triarnine. cast iron. of additives. The reaction product of longchain fatty acids with di- 98. 5 do -do 8.7 No significant change inethylene triamine and 2 mols of ethylene oxide. weatr a? compared to conr0 The reaction product of long chain fatty acids with dipro- 98. 5 .dodo 5. 5 4.3.

pylene triamine plus 2 mols of ethylene oxide. I The reaction product oflong chain fatty acids and dipro- 98. 5 ..-do .-do 5. 5 No significantchange in pylene triamine.

A commercial mixture comprising about to percent by weight ofl-(Zaminoethyl)-2-heptadecenylimidazoline (Ci7)C--NCH2CH2NHg 0 A mixturecontaining in major proportion and/or corresponding imidazolines havingtwo separate hydroxycthyl groups attached to the side chain nitrogen.

wear as compared to control.

0 A mixture containing in major proportion and methyl isomers thereof,and/or corresponding imidazolines having two separate hydroxyethylgroups attached to the side chain nitrogen.

d A mixture containing in major proportion and methyl isomers thereof.

7 EXAMPLE 3 A'further series of tests was conducted which utilized amethod other than radioactivity to determine not only antiwearcharacteristics" but also engine cleanliness characteristics of adisubstituted imidazoline in gasoline. The

Test procedure The test is performed with a 216 cu. in. 6-cylinderautomobile engine in five 8-hour test periods. Following each of thefirst four periods of operation the engine is shut down for a 4-hourinterval. Preceding the first 8- hour test period there is a progressivebreak-in over a 4-hour period in order to attain test conditions by theend of the last hour of the break-in period. At the end of the break-inperiod the crankcase oil is drained, the crankcase refilled and theengine operated for a 10-minute warm-up before commencing the first8-hour period of test operation.

Following are the conditions prevailing during the test:

Load: BHP 45:1.

Speed: r.m.p. 2500:25.

Spart advance 38:3 before top center at 2500 r.p.m.

Spark plug gap: in. 0.040.

Va-lve clearances-in:

Intake 0.008.

Exhaust 0.013.

Intake manifold Heat control locked in off position. Pistons Tin platedcast iron.

Water jacket coolant temperature:

Inlet: F. 85:5.

Outlet: F. 95:2.

Oil temperature: F. 155:5.

Air-fuel ratio l4.5:0.5/ 1.0.

Crankcase ventilation: c.f.m. 1.

Oil change: qt. 4 /2.

Crankcase lubricant Motor oil.

At the end of the test, the engine is disassembled and rated visuallyfor deposits on the following parts to establish the total enginecleanliness rating.

Varnish Deposits: Sludge deposits:

Piston Skirts Oil Screen Cylinder Walls Crankcase Oil Pan Crankcase OilPan Rocker-Arm Assembly PushaRod Cover Plate Rocker-Arm Cover PlateRocker-Arm Cover Plate Push-Rod Cover Plate The total engine rating isthe sum of the ratings made on the ten parts listed above. Each part israted on a scale of (heavy deposits) to (clean).

The piston rings were weighed before and after the test to ascertain thering weight loss. The results of the test are shown in Table 3.

TABLE 3.EFFECT OF ADDITIVE ON ENGINE OLEANLINESS AND WEAR Fuel make-up,percent by volume:

G olme 100 100 5 Added:

Tetraethyl lead, mL/gaL 2. 5 2. 5 The reaction product of long chainfatty acids and diethylene triamine, lbs/1,000 bbls Oil make-up, percentby volume:

Light neutral oil 30. 25 Medium neutral oil .0 65. 00 Oil additive b 4.25 10 on additive 0. 50 Oil additive 0. 01 ti-cylinder automobile enginecleanliness and wear test:

Total engine cleanliness rating (l00=clcan) (varnish and sludge) "80. 082. 0 Skirt varnish rating avg. piston (10=clean) 6. 5 7. 5 Ring weightloss: 1 First ring (compression): Average weight loss 1 for six pistons,mg .9 68

Second ring: Average weight loss for six pistons,

mg 34 f Third ring: Average weight loss for six pistons,

mg 54 s 34 Total average ring Weight loss, mg 180 132 I! A commercialmixture comprising about 90 to 95 percent by weight oil-(2-aminocthyl)-2-hcptadecenylimidazoline v v Commercial antioxidant,bearing corrosion inhibitor detergent comprising barium sulfonatc,barium phosphonate, zinc dialkyl dithiophosphate and anitrogen-containing compound.

0 Commercial detergent, pour point depressant and viscosity indeximprover.

Commercial antifoam agent comprisinga silicone polymer.

9 26% reduction in wear.

f 12% reduction in wear.

B 37% reduction in wear.

h 27% reduction in wear.

Table 3 shows the high utility of an additive of *thisinvention forpurposes of both maintaining engine cleanliness and reducing piston ringwear.

The tests of Examples 4 and 5 were conducted to il lustrate theimprovement imparted to gasoline by lecithin mixtures with disubstitutedimidazolines. and lecithin derivatives of disubstituted imidazolines inregard to fuel filter-clogging characteristics.

EXAMPLE 4 Table 4 shows the results of gasoline circulation tests todetermine the maximum possible throughput through of fuel filter until a50 percent reduction in fuel flow rate through the filter elementoccurred. The tests were conducted with a gasoline control sample andwith gasoline containing a lecithin-free disubstituted imidazoline.

TABLE 4.GASOLINE CIRCULATION TESTS Fuel make-up, percent by volume:

Gasoline 100 100 Added: J

Tetraethyl lead: ml. /gal 2. 5 2. 5 Solvent oil, percent by volume 0.5The reaction product of long chain fatty acids and diethylene triamine,lbs/1,000 131315;. 15 Circulation test Fuel throughput in gallons untilthere is a 50 percent reduction in flow rate through filter 20 5filter-clogging characteristics of gasoline. 1'

EXAMPLE 5 A further series of gasoline filter-clogging tests wereconducted to illustrate the improvement imparted to gasoline in thisrespect by lecithin mixtures with and derivatives of a disubstitutedimidazoline. These tests were conpercent by weight of ducted withgasoline containing lecithin alone, with gasoline containing a lecithinmixture with disubstituted imidazoline and with gasoline containing alecithin derivative of disubstituted imidazoline. The results of thesetests are shown in Table 5. In reference to the data of Table 5, it isnoted that a gasoline is considered to exhibit satisfactoryfilter-clogging performance when there is less than 50 percent reductionin fuel fiow rate through a filter element at 20 gallons throughput.

TABLE 5.-GASOLINE CIRCULATION TESTS Additives:

Lecithin Reaction product of lecithin and the reaction product of longchain fatty acids and diethylene triamine Mixture of lecithin and thereaction product of long chain fatty acids and diethylene triamine bGasoline tests:

Gasoline circulation test percent reduction in flow rate at statedgallons fuel throughput (more than 50 percent reduction in flow rate at20 gallons fuel throughput is unsatisfactory) Intake System Deposit Testpercent reduction in carburetor-type gum deposits 1 50% at -15 gals. 225% at 20 gals. B 22% at 20 gals.

e A commercial neutral oil solution of a filtered soybean lecithin withmoisture value less than 0.75 percent by Weight, an acetoneinsolublevalue of 70 percent by Weight and a viscosity of 3,046 centipoises.

b A commercial mixture comprising about 90 to 95 percent by Weight ofl-(2-aminoethyl)-2-heptadecenylimidazoline (Cm-g III-CHzCH2NHg N CH2 Forthe Gasoline Circulation Tests additive concentrations were lbs. per1,000 barrels of gasoline plus 0.5 percent by volume solvent oil.Gasoline Circulation Test procedure is described in SAE Reprint No. 610B, G. E. Gaston and J. J. Thomas, Contribution of Sediment and Additivesin Gasoline to Clogging of Filters in Automotive Fuel Systems, presentedat Philadelphia, Pennsylvania, Meetings, October 29- November 2, 1962.

d For the Intake System Deposit Tests the concentration of additives Was15 lbs. per 1,000 barrels of gasoline. The test simulates deposition ofgum carried by gasoline in a carburetor and involves forming a gumdeposit in a test apparatus by evaporating additive-containing, high gumcontent fuel flowing counterourrent to a stream of heated air. At theend of the test, the Weight of the adhering gum is determined andcompared to a reference run Without additive for an appraisal of theadditives detergency action. The test employs the same apparatusdescribed by J. L. Keller and F. S. Liggett, Induction System Gum-EngineVersus Bench Test, Symposium onVapor Phase Oxidation of Gasoline, ASTMSpecial Technical Publication No. 202, pp. 21-40 (1956), but a somewhatdifferent procedure is employed in order to appraise detergency actionof additives. A gum deposit is formed on the Walls of a steam-jacketedglass U-tube by evaporating two liters of gasoline distillate admittedto the system countercurrent to a stream of preheated air. The U-tube isthen washed with a number of portions of naphtha until a final washshows no discoloration. The amount of gum adhering to the apparatus isthen determined by extracting with 0.1. acetone and evaporating theacetone extract with filtered, heated air to obtain a gum residue whichis heated in an oven for one-half hour at 100105 C., cooled and Weighed.Results of runs using the same gasoline with and Without additive arecompared to determine detergency action.

As noted above, satisfactory filter-clogging performance is achievedwhen there is less than 50 percent reduction in the fuel flow ratethrough a filter element at gallons throughput. The data in Table 4indicate that disubstituted imidazoline Without lecithin did not producea gasoline composition meeting this filter-clogging perform- 5 ancerequirement. Also, Table 5 shows that lecithin without imidazoline didnot produce a gasoline composition meeting this filter-cloggingperformance requirement. However, Table 5 shows that both the mixture oflecithin with disubstituted imidazoline and the lecithin derivatives ofdisubstituted imidazoline produced a gasoline compo sition which easilysatisfied required filter-clogging performance levels. Table 5 alsoshows that use of either the mixture of lecithin with disubstitutedimidazoline or the lecithin derivative of disubstituted imidazolineresulted in reduced formation of carburetor-type gum deposits ascompared to the performance of lecithin alone in this regard.

Various changes and modifications can be made without departing from thespirit of this invention or the scope thereof as defined in thefollowing claims.

I claim:

1. The reaction product of a 1,2-disubstituted imidazoline having theformula wherein R is alkyl/or alkenyl containing 7 to 29 carbon atoms, Ris a methylene group or an ethylene group, and R and R are hydrogen,methyl or ethyl radicals, with lecithin, the reaction occurring at 40 toC. with a ratio of lecithin to imidazoline between about 1 to 20 andabout 20 to 1. 2. The reaction product of claim 1 wherein R contains 11to 17 carbon atoms, R is an ethylene group, and R and R are hydrogen.

References Cited UNITED STATES PATENTS 2,355,837 8/1944 Wilson 260-309.6

2,794,808 6/1957 Albrecht et al. 260-309.6

3,291,731 12/1966 Crowley et a1. 260-309.6

3,313,607 4/1967 Gaston 44-58 FOREIGN PATENTS 846,693 8/ 1960 GreatBritain 44-58 OTHER REFERENCES Hackhs Chemical Dictionery, 4th ed.(1969) ed. Julius Grant, p. 384.

HENRY R. JILES, Primary Examiner S. D. WINTERS, Assistant Examiner U.S.Cl. X.R. 44-63

